WO2001042227A1 - Composes de difluoromethyltriazolone, utilisation de ces composes et intermediaires pour leur fabrication - Google Patents

Composes de difluoromethyltriazolone, utilisation de ces composes et intermediaires pour leur fabrication Download PDF

Info

Publication number
WO2001042227A1
WO2001042227A1 PCT/JP2000/008558 JP0008558W WO0142227A1 WO 2001042227 A1 WO2001042227 A1 WO 2001042227A1 JP 0008558 W JP0008558 W JP 0008558W WO 0142227 A1 WO0142227 A1 WO 0142227A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alkyl
methyl
alkoxy
formula
Prior art date
Application number
PCT/JP2000/008558
Other languages
English (en)
Japanese (ja)
Inventor
Tomohiro Araki
Yoshiharu Kinoshita
Hiroshi Sakaguchi
Akio Manabe
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to US10/149,034 priority Critical patent/US6762197B2/en
Priority to EP00979060A priority patent/EP1238975A1/fr
Priority to AU16510/01A priority patent/AU1651001A/en
Publication of WO2001042227A1 publication Critical patent/WO2001042227A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C07C309/66—Methanesulfonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to a triazolone compound, its use, and an intermediate for its production.
  • the present invention provides a compound having a bactericidal activity, particularly an excellent bactericidal activity against a fungus which causes a plant disease, and which is useful for controlling a plant disease. That is, the present invention provides the following formula:
  • R 1 is an A 1 — L 1 — group
  • a 1 — ⁇ N CA 2 — group
  • a 1 — C (A 2 ) N— OCH 2 — group
  • a 1 S _C (A 2 ) N—group
  • a 1 S—C ( S) NH—group
  • a 1 S—C (SA 2 ) N—group
  • C (Me) CH 2 ⁇ N C (CN) — group
  • a 1 — C (CN) N— OCH 2 — group, halogen atom, nitro group or cyano group
  • a 1 and A 2 are the same or different and are a hydrogen atom, a C 1 -C 10 alkyl group, a C 2 -C 10 alkenyl group, a C 2 -C 10 alkynyl group, a C 3 -C 10 cycloalkyl Group, (C3-C10 cycloalkyl) CI- (: 10 alkyl group, C5-C10 cycloalkenyl group, (C5-C10 cycloalkenyl) C1-C10 alkyl group, phenyl group , A naphthyl group, a phenyl C 1-(: 10 alkyl group, a naphthyl C 1-C 10 alkyl group, a 5- or 6-membered heterocyclic group which may be fused with a benzene ring, or a fused benzene ring Represents a methyl group substituted by a 5- or 6-membered heterocyclic group, wherein A 1 and A 2
  • T is an optionally substituted metaphenylene group, an optionally substituted metaazaphenylene group (metapyridinediyl group) bonded to each of R 1 and CH 2 with a carbon atom, or an optionally substituted metadiazaphenyl group;
  • Represents a diene group (metaziazinezyl group, ie, a metapyridazinediyl group, a metapyrimidinediyl group or a metapyrazindiyl group), wherein these substituents are a halogen atom, a cyano group, Toro group, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group, C1-C6 It is at least one substituent selected from the group consisting of a haloalkylthio group and a (C1-C5 al
  • the present invention further provides a compound of the formula [L] useful as an intermediate for producing the compound of the present invention.
  • R 9 represents a methyl group or a P-tolyl group.
  • Inorganic acid salts of N, N-dimethyl (2-methyl-5-phenylpentyl) amine and N, N-dimethyl (2-methyl-5-phenylpentyl) amine represented by eg, hydrochloric acid addition salt, hydrobromic acid
  • addition salts, sulfuric acid addition salts) and sulfonic acid salts eg, methanesulfonic acid addition salts.
  • the C 1 -C 10 alkyl groups represented by A 1 and A 2 include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1-methylpropyl, pentyl Group, 1-methylbutyl group, 1-ethylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, hexyl Group, 1-methylpentyl group, 1-ethylpentyl group, 3,3-dimethylbutyl group, heptyl group, 3,7-dimethyloctyl group, and the like.
  • Examples of the C 2 -C 10 alkenyl group include a vinyl group and an aryl group.
  • a C2-C10 alkynyl group includes Examples thereof include an ethyl group, a propargyl group, a 1-methyl-2-propynyl group, and a 2-butynyl group.
  • Examples of the C3-C10 cycloalkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
  • Examples of the (C3-C10 cycloalkyl) alkyl group include a cyclopropylmethyl group, a cyclopentylmethyl group, a 2-cyclopentylethyl group, a cyclohexylmethyl group, and the like.
  • Examples of the -C 10 cycloalkenyl group include a cyclopentenyl group and a cyclohexenyl group.
  • Examples of the (C 5 -C 10 cycloalkenyl) alkyl group include Pentene-1-ylmethyl group, cyclohexene_l_l-l-methyl group and the like; phenyl ci-cioalkyl groups include, for example, phenylmethyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl Examples of the naphthyl C 1 -C 10 alkyl group include an a-naphthylmethyl group and a / 3-naphthylmethyl group, and a 5- or 6-membered benzene ring may be condensed.
  • heterocyclic group examples include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 2-virazinyl group, 3-pyridazinyl group, and 4-— Pyridazinyl, 2-phenyl, 3-phenyl, 2-furyl, 3-furyl, pyrrole-1-yl, pyrroyl-2-yl, pyrroyl-3- 1-pyrazolyl group, 3-pyrazolyl group, 4-pyrazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-oxazolyl group, 4-year-old xazolyl group, 5-year-old xazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 1-
  • alkoxy group examples include a methoxy group, an ethoxy group and a propoxy group. Cis, isopropoxy, butoxy, sec-butoxy, isobutoxy, pentyloxy, etc.
  • haloalkoxy group examples include trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy. Chlorodifluoromethoxy group, fluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, and the like.
  • alkylthio group examples include: Methylthio, ethylthio, propylthio, butylthio, isobutylthio, sec-butylthio, pentylthio, hexylthio and the like.
  • haloalkylthio groups include trifluoromethylthio, difluoromethylthio and the like. , Bromodifluoromethylthio, chlorodifluoromethy A thio group, a fluoromethylthio group, a 2,2,2-trifluoroethylthio group, a 1,1,2,2-tetrafluoroethylthio group, and the like.
  • alkylcarbonyl group examples include: Examples thereof include an acetyl group, a propanol group, a butanol group, and a 3-methylbutanol group.
  • alkoxycarbonyl group examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, and a butoxy group.
  • Examples of the C3-C20 trialkylsilyl group include 3-methylbutyrylamino group and the like, and examples thereof include a trimethylsilyl group and a triethylsilyl group.
  • the phenyl group, naphthyl group of A 1 and A 2 the benzene ring in the phenylalkyl group, the naphthylene ring in the phenylnaphthyl group, the heterocyclic group and the heterocyclic group of the methyl group substituted by the heterocyclic group
  • the ring is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a nitro group, a C1-C10 alkyl group, a C1-C10 haloalkyl group, a C3-C 10 cycloalkyl group, C1-C10 alkoxy group, C1- (: 10 haloalkoxy group, C1-C10 alkylthio group, C1-C10 haloalkylthio group, (C1-C (C 1 -C 9 alkoxy) carbonyl, (C 1 -C 9
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 1-methylpropyl group, a pentyl group, 1-methylbutyl group, 1-ethylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, hexyl group, 1- Methylpentyl, 1-ethylpentyl, 3,3-dimethylbutyl, heptyl, 3,7-dimethyl Octyl group and the like.
  • haloalkyl group examples include trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group and the like.
  • cycloalkyl group examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.
  • Each of a methylenedioxy group and a difluoromethylenedioxy group is a benzene ring, a naphthylene ring or Substitutes two adjacent carbon atoms on the heterocycle.
  • a phenylene group and a metadiazaphenylene group are a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, and a C1- It may be substituted by a C 6 alkoxy group, a C 1 -C 6 haloalkoxy group, a C 1 -C 6 alkylthio group, a C 1 -C 6 haloalkylthio group or a (C 1 -C 5 alkoxy) carbonyl group.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • Examples of the alkyl group include a methyl group and an ethyl group
  • examples of the haloalkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a methyl group. Examples thereof include a methoxy group and an ethoxy group.
  • examples of the haloalkoxy group include a trifluoromethoxy group, a difluoromethoxy group and a prodifluoromethoxy group. Methoxy, chlorodifluoromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, and the like.
  • Examples of the alkylthio are methylthio.
  • haloalkylthio groups such as trifluoromethylthio, difluoromethylthio, bromodifluoromethylthio, chlorodifluoromethylthio, fluoromethylthio, 2,2,2 —Trifluoroethylthio group, 1,1,2,2-tetrafluoroethylthio group and the like.
  • alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
  • R 1 may be a substituted phenyl group (that is, R 1 is an A 1 —L 1 — group, L 1 is a single bond, and A 1 may be substituted
  • a compound represented by the following formula is preferable because of excellent bactericidal effect.
  • T a compound represented by a metaphenylene group or a substituted metaphenylene group is preferable in terms of having an excellent bactericidal effect, and preferable substituents are a methyl group, a fluorine atom, a chlorine atom and a trifluoromethyl group. Oromethyl group.
  • the compound of the present invention can be produced, for example, according to the following Production Methods A to G. Also, depending on the content of R 1, can also child introduced or build the desired R 1 to the end (for example, Process H). In these production methods, a protecting group can be used as needed to protect the functional group from the reaction.
  • the reaction temperature of the reaction for obtaining the compound of the present invention of the formula [I] from the formyl compound of the formula [II] is usually in the range of 120 to 100 ° C, and the reaction time is usually 10 Within the range of minutes to 10 hours.
  • the amount of getylaminosulfur trifluoride to be subjected to the reaction is usually 1 to 20 mol per 1 mol of the formyl compound represented by the formula [II].
  • the reaction is usually carried out in a solvent.
  • the solvent used include halogenated hydrocarbons such as chloroform and benzene, ethers such as 1,4-dioxane, tetrahydrofuran, and getyl ether;
  • halogenated hydrocarbons such as chloroform and benzene
  • ethers such as 1,4-dioxane, tetrahydrofuran, and getyl ether
  • examples thereof include aliphatic hydrocarbons such as hexane and petroleum ether, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
  • reaction solution After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as washing with a sodium bicarbonate solution and then concentrating the organic layer to isolate the target compound.
  • a post-treatment operation such as washing with a sodium bicarbonate solution and then concentrating the organic layer to isolate the target compound.
  • the target compound can be purified by recrystallization, chromatography or the like.
  • the formyl compound represented by the formula [II] can be produced, for example, according to the following scheme.
  • R 1 and T represent the same meaning as described above, and L 2 represents a chlorine atom, a bromine atom, an iodine atom, a ⁇ -toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, etc.
  • R 5 represents a C 1 -C 5 alkyl group (eg, a methyl group, an ethyl group, etc.), a phenyl group or a trihaloethyl group (eg, a trichloroethyl group, etc.).
  • the semicarbazide compound represented by the formula [VII] can be produced by reacting the isocyanate compound represented by the formula [III] with methylhydrazine.
  • the reaction temperature of the reaction is usually in the range of 20 to 50 ° C, and the reaction time is usually in the range of 1 to 100 hours.
  • the amount of methylhydrazine used for the reaction is usually 1 to 10 mol per 1 mol of the isocyanate compound represented by the formula [III].
  • the reaction is carried out in a solvent if necessary, and the solvent used
  • ethers such as 1,4-dioxane, tetrahydrofuran, and getyl ether
  • halogenated hydrocarbons such as chloroform and benzene
  • aliphatic hydrocarbons such as hexane and petroleum ether
  • toluene And aromatic hydrocarbons such as xylene, amides such as N, N-dimethylformamide, dimethylsulfoxide and the like, and mixtures thereof.
  • the reaction solution is subjected to a post-treatment operation such as concentration to isolate a target compound.
  • the target compound can be purified by recrystallization, chromatography or the like.
  • the semicarbazide compound represented by the formula [VIII] can be produced by reacting the isocyanate compound represented by the formula [III] with 1-methyl-2-hydroxyacetylhydrazine in the same manner as described above.
  • the semicarbazide compound represented by the formula [IV] can be produced by reacting the isocyanate compound represented by the formula [III] with hydroxyacetylhydrazine in the same manner as described above.
  • the compound represented by the formula [V] can be obtained by reacting a semicarbazide compound represented by the formula [IV] with a base. For example, a compound represented by the formula [V] is treated with an aqueous hydration power solution. Can be obtained.
  • the compound represented by the formula [VI] can be obtained by reacting a semicarbazide compound represented by the formula [VIII] with a base.
  • a compound represented by the formula [VI] is treated with an aqueous hydration-reactive aqueous solution. Can be obtained.
  • the compound represented by the formula [VI] can be obtained by reacting the compound represented by the formula [V] with a base.
  • a base examples include potassium carbonate.
  • the compound represented by the formula [II] can be obtained by oxidizing the compound represented by the formula [VI].
  • the oxidizing agent used include manganese dioxide.
  • the isocyanate compound represented by the formula [III] can be produced, for example, according to the following scheme. reduction
  • R 6 represents a C 1 -C 4 alkyl group (eg, a methyl group, an ethyl group, etc.)
  • M 1 represents silver or sodium
  • BuLi represents butyllithium
  • DMF represents N, N-dimethylformamide.
  • METHOD reaction for example to the original place of lithium aluminum hydride (L i A l H 4) to obtain the amine of compound of formula by reducing a nitrile compound represented by [XV] wherein [XVI], the catalyst It can be carried out by, for example, hydrogenating the nitrile compound represented by the formula [XV] in the presence.
  • the catalyst used for hydrogenation include Raney nickel, palladium and the like. The method using Raney nickel is disclosed in JP-A-8-291116, and the method using palladium is described in J. Am. Che. m. So, 50, 3370 (1928), respectively.
  • the reaction of obtaining a compound represented by the formula [ ⁇ ] wherein L 2 is a chlorine atom from the alcohol compound represented by the formula [ ⁇ ] is carried out, for example, by adding an alcohol compound represented by the formula [XII] to CC 14-PPh3 (Specifically, the method described in Intermediate Production Example 9 described later), and a method of allowing concentrated alcohol to act on the alcohol compound represented by the formula [XII] (Org. Synth., IV, 576 (1967) See)).
  • L 2 is a bromine atom or an iodine atom.
  • the reaction for obtaining the amine compound represented by the formula [XVI] from the compound represented by the formula [XI II] can be performed, for example, according to the method described in J. Org. Cem., 58, 270 (1993). .
  • ⁇ Can also be produced from the benzyl chloride compound represented by the formula [XVII] according to the following chemical reaction formula.
  • R 1Q represents a substituent that is inactive in a Grignard reaction among the substituents defined for R 1 .
  • the reaction is carried out in a solvent, and the solvents used are: Examples thereof include ethers such as trahydrofuran, diglyme, and triglyme, and mixed solvents of the ethers and aromatic hydrocarbons such as toluene and xylene. If necessary, for example, J. Am. Chem. Soc, 73, 3237 (1951) can be referred to.
  • 2-methyl-5-phenylpentyl chloride represented by the formula [XIII-1] can also be produced according to the following scheme.
  • L 2 has the same meaning as described above, and R 11 represents a C 1 -C 4 alkyl group (eg, a methyl group, an ethyl group, etc.) or a vinyl group. ]
  • the reaction for obtaining the compound represented by the formula [LI II] from the compound represented by the formula [LII] can be performed, for example, according to the method described in Tetrahedron, 50, 13697 (1994).
  • the reaction for obtaining N, N-dimethyl- (2-methyl-5-phenylbenzyl) amine represented by the formula [LI] from the compound represented by the formula [LIII] is described, for example, in Organic Reactions, 18, 403-464 (1970).
  • Examples of the base used in the reaction include sodium hydride, potassium hydride, sodium amide, potassium amide, phenyllithium, butyllithium and the like.
  • the compound of the present invention represented by the formula [I] can be produced from the triazolone compound represented by the formula [XIX] according to the following chemical reaction formula.
  • the reaction is usually performed in the presence of a base, and examples of the base used include inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
  • the reaction temperature of the reaction for obtaining the compound of the present invention represented by the formula [I] from the triazolone compound represented by the formula [XIX] is usually within a range from 120 to 100, and the reaction time is usually from 1 to 100. Within 100 hours.
  • the amount of the reagent used in the reaction is usually 1 to 5 mol of the methylating agent of the formula [IX] and 1 to 1 mol of the methylating agent of the formula [IX] to 1 mol of the triazolone compound of the formula [XIX]. 0 mole ratio.
  • the reaction is carried out in a solvent, if necessary.
  • solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, t-butyl methyl ether, hexane, heptane, and rig.
  • Aliphatic hydrocarbons such as ketones and petroleum ethers, aromatic hydrocarbons such as toluene and xylene, organic bases such as pyridine, triethylamine, N-methylaniline, N, N-dimethylaniline, and N, N-jethylaniline And nitriles such as acetonitrile and isobutyronitrile, N, N-dimethylformamide, dimethylsulfoxide, water and the like, and mixtures thereof. These solvents are used depending on the type of base used. After completion of the reaction, the reaction solution is subjected to ordinary post-treatment operations such as extraction with an organic solvent, concentration, and the like. The target compound is isolated. The target compound can be purified by recrystallization, chromatography or the like.
  • the starting triazolone compound represented by the formula [XIX] can be produced, for example, according to the following scheme.
  • the isothiocyanate compound represented by the formula [XXI] can be produced by reacting a compound represented by the formula [XIII] with a compound represented by the formula [XX].
  • the thiosemicarbazide compound represented by the formula [XXII] can be produced by reacting the isothiocyanate compound represented by the formula [XXI] with hydrazine (anhydrous hydrazine or hydrazine hydrate).
  • the triazolinethione compound represented by the formula [XXIII] can be produced by reacting the thiosemicarbazide compound represented by the formula [XXII] with difluoroacetic acid.
  • the sulfonic acid compound represented by the formula [XXIV] can be produced by oxidizing the triazolinethione compound represented by the formula [XXIII] using an oxidizing agent (for example, hydrogen peroxide).
  • the triazolone compound represented by the formula [XIX] can be produced by hydrolyzing a sulfonic acid compound represented by the formula [XXIV] using an acid (for example, hydrochloric acid).
  • an acid for example, hydrochloric acid
  • the reaction solution should be subjected to ordinary post-treatment operations such as extraction with an organic solvent and concentration.
  • the target compound is isolated.
  • the target compound can be purified by recrystallization, chromatography or the like.
  • the compound of the present invention represented by the formula [I] can be produced from the semicarbazide compound represented by the formula [VI I], for example, according to the following chemical reaction formula.
  • reaction temperature of the above reaction for obtaining the compound of the present invention represented by the formula [I] from the semicarbazide compound represented by the formula [VI I] is usually in the range of 120 to 100: and the reaction time is usually Within the range of 1 to 100 hours.
  • the amount of the reagent used in the reaction is usually 1 to 5 mol of difluoroacetic anhydride per 1 mol of the semicarbazide compound represented by the formula [VII].
  • the reaction is usually carried out in a solvent.
  • solvent examples include aromatic hydrocarbons such as toluene and xylene, ethers such as 1,4-dioxane, tetrahydrofuran and getyl ether, hexane, petroleum ether and the like. Aliphatic hydrocarbons or mixtures thereof.
  • a difluoroacetyl semicarbazide compound represented by the following formula [XXVI] may be generated as a by-product, but can be separated and removed by purifying the target compound by chromatography or the like.
  • the separated difluoroacetylsemicarbazide compound represented by the formula [XXVI] can be used as a starting material in Production Method F described below.
  • the reaction mixture is subjected to a post-treatment operation such as extraction with an organic solvent and concentration after the excess difluoroacetic anhydride is decomposed with a base such as aqueous sodium hydroxide solution to isolate the target compound.
  • a post-treatment operation such as extraction with an organic solvent and concentration after the excess difluoroacetic anhydride is decomposed with a base such as aqueous sodium hydroxide solution to isolate the target compound.
  • a base such as aqueous sodium hydroxide solution
  • the target compound can be purified by recrystallization, chromatography or the like.
  • Manufacturing method D The compound of the present invention represented by the formula [I] can be produced from the semicarbazide compound represented by the formula [VI I], for example, according to the following chemical reaction formula.
  • R 1 and T have the same meanings as described above, and R 7 represents a C: C 4 alkyl group (eg, a methyl group, an ethyl group, etc.). ]
  • the reaction temperature of the above reaction for obtaining the compound of the present invention represented by the formula [I] from the semicarbazide compound represented by the formula [VI I] is usually in the range of 20 to 100 ° C., and the reaction time is usually 1 to 10 ° C. Within the range of ⁇ 100 hours.
  • the amount of the reagent to be subjected to the reaction is usually a ratio of 1 to: L00 mol of the compound represented by the formula [XXV] to 1 mol of the semicarbazide compound represented by the formula [VII].
  • the reaction is carried out in the presence of a base.
  • the base used include metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Examples thereof include alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and organic bases such as triethylamine and pyridine.
  • the amount of the base is usually 1 mol of the semicarbazide compound represented by the formula [VI I]. The ratio is 0.1 to 3 moles with respect to the total.
  • the reaction is carried out in a solvent if necessary.
  • solvent used include alcohols such as methanol and ethanol, ethers such as 1,4-dioxane, tetrahydrofuran and diethyl ether, and aliphatic hydrocarbons such as hexane and petroleum ether. Hydrogens, aromatic hydrocarbons such as toluene and xylene, amides such as N, N-dimethylformamide, dimethylsulfoxide and the like, and mixtures thereof.
  • a difluoroacetyl semicarbazide compound represented by the following formula [XXVI] may be generated as a by-product, but can be separated and removed by purifying the target compound by chromatography or the like.
  • the separated difluoroacetylsemicarbazide compound represented by the formula [XXVI] was prepared as described below. Can be used as a starting material for Law F.
  • reaction solution is neutralized or concentrated as necessary, and then subjected to a post-treatment operation such as extraction with an organic solvent and concentration to isolate the target compound. Further, the target compound can be purified by recrystallization, chromatography and the like.
  • the compound of the present invention represented by the formula [I] can be produced from the semicarbazide compound represented by the formula [VI I], for example, according to the following chemical reaction formula.
  • the reaction temperature of the above reaction for obtaining the compound of the present invention represented by the formula [I] from the semicarbazide compound represented by the formula [VI I] is usually in the range of 20 to 100 ° C., and the reaction time is usually 1 to 10 ° C. Within the range of ⁇ 100 hours.
  • the amount of the reagent used for the reaction is usually 1 to 100 mol of difluoroacetic acid per 1 mol of the semicarbazide compound represented by the formula [VII].
  • the reaction is carried out in a solvent as necessary.
  • solvent examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and petroleum ether, and 1,4-dioxane. And ethers such as tetrahydrofuran and the like, and mixtures thereof.
  • a difluoroacetyl semicarbazide compound represented by the following formula [XXVI] may be generated as a by-product, which can be separated and removed by purifying the target compound by chromatography or the like.
  • the separated difluoroacetylsemicarbazide compound represented by the formula [XXVI] can be used as a starting material in Production Method F described below.
  • the reaction solution is neutralized or concentrated as necessary, and then subjected to a post-treatment operation such as extraction with an organic solvent and concentration to isolate the target compound. Further, the target compound can be purified by recrystallization, chromatography and the like. Manufacturing method F
  • the compound of the present invention represented by the formula [I] can be produced from a difluoroacetylsemicarbazide compound represented by the formula [XXVI], for example, according to the following chemical reaction formula.
  • the reaction temperature of the reaction for obtaining the compound of the present invention represented by the formula [I] from the difluoroacetylsemicarbazide compound represented by the formula [XXVI] is usually in the range of 20 to 100 ° C, and the reaction time is Usually in the range of 10 minutes to 10 hours.
  • the reaction is carried out in the presence of a base or an acid.
  • the base used include metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; Examples include metal hydroxides, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and organic bases such as triethylamine and pyridine.
  • the amount of the base used is usually 0.1 to 10 mol per 1 mol of the difluoroacetylsemicarbazide compound represented by the formula [XXVI].
  • the acid used include organic acids such as difluoroacetic acid and trifluoroacetic acid.
  • the amount of the acid used is generally 1 to 10 with respect to 1 mol of the difluoroacetylsemicarbazide compound represented by the formula [XXVI]. 0 mole ratio.
  • the reaction is carried out in a solvent as necessary.
  • the solvent used include alcohols such as methanol and ethanol, ethers such as 1,4-dioxane, tetrahydrofuran and getyl ether, hexane and petroleum ether. And aliphatic hydrocarbons such as toluene and xylene; amides such as N, N-dimethylformamide; sulfoxides such as dimethylsulfoxide; water; and mixtures thereof. These solvents can be used depending on the type of acid or base used.
  • the reaction solution is neutralized or concentrated as necessary, and then subjected to a post-treatment operation such as extraction with an organic solvent and concentration to isolate the target compound. Further, the target compound can be purified by recrystallization, chromatography or the like.
  • the difluoroacetylsemicarbazide compound represented by the formula [XXVI] can be obtained as a by-product in Production Methods C, D and E, and can be produced, for example, according to the following scheme.
  • the reaction temperature for obtaining the difluoroacetylsemicarbazide compound represented by the formula [XXVI] from the isocyanate compound represented by the formula [III] is usually in the range of 0 to 10 ° C, and the reaction time is usually 1 to 10 ° C. Within 10 hours.
  • the amount of N′-methyldifluoroacetohydrazide to be subjected to the reaction is usually 1 to 10 mol per 1 mol of the isocyanate compound represented by the formula [III].
  • the reaction is carried out in a solvent as necessary.
  • the solvent used include ethers such as 1,4-dioxane, tetrahydrofuran, and acetyl ether; octogenated hydrocarbons such as chloroform and benzene.
  • ethers such as 1,4-dioxane, tetrahydrofuran, and acetyl ether
  • octogenated hydrocarbons such as chloroform and benzene.
  • aliphatic hydrocarbons such as xane and petroleum ether, aromatic hydrocarbons such as toluene and xylene, amides such as N, N-dimethylformamide, dimethyl sulfoxide and the like, and mixtures thereof.
  • the reaction mixture is subjected to post-treatment operations such as concentration, extraction with an organic solvent, and concentration to isolate the target compound.
  • the target compound can also be purified by recrystallization, chromatography or the like.
  • the compound of the present invention represented by the formula [I] includes a compound represented by the formula [XIII] and a compound represented by the formula [L] Can be produced from the triazolone compound represented by the following formula, for example, according to the following chemical reaction formula.
  • the reaction is carried out in the presence of a base.
  • a base examples include inorganic bases such as lithium hydroxide, lithium hydride, sodium hydroxide, sodium hydride, potassium hydroxide, potassium hydride, sodium carbonate, and potassium carbonate. Bases and the like can be mentioned.
  • the reaction temperature is usually in the range of 0 to 100, and the reaction time is usually in the range of 1 to 100 hours.
  • the amount of the reagent used in the reaction is usually 1 to 5 mol of the triazolone compound represented by the formula [L] and 1 mol of the base represented by 1 mol of the compound represented by the formula [ ⁇ ⁇ ].
  • the ratio is 1 to 10 mol.
  • the reaction is carried out in a solvent as necessary.
  • the solvent used include ethers such as 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, aromatic hydrocarbons such as toluene and xylene, pyridine, Organic bases such as triethylamine, N-methylaniline, N, N-dimethylaniline, N, N-getylaniline, nitriles such as acetonitrile, isobutyronitrile, N, N-dimethylformamide, dimethylsulfoxide, water, etc. Mixtures. These solvents are used depending on the type of base used.
  • reaction solution After completion of the reaction, the reaction solution is subjected to post-treatment operations such as extraction with an organic solvent and concentration to isolate the target compound.
  • the target compound can be purified by recrystallization, chromatography or the like.
  • the triazolone compound represented by the formula [L] can be produced, for example, according to the following chemical reaction formula.
  • the reaction temperature for obtaining the triazolone compound represented by the formula [L] from 2-methylsemicarbazide is usually in the range of 50 to 150 ° C, and the reaction time is usually in the range of 1 to 100 hours. It is.
  • the amount of the reagent used in the reaction is usually 1 to 100 mol of difluoroacetic acid per 1 mol of 2-methylsemicarbazide.
  • the reaction is carried out in a solvent, if necessary.
  • solvent examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and petroleum ether, 1,4-dioxane, tetrahydrofuran and the like. Ethers or mixtures thereof.
  • 1-difluoroacetyl-2-methylsemicarbazide may be obtained as a by-product, but it can be separated and removed by purification by chromatography or the like.
  • reaction solution is neutralized or concentrated, if necessary, and then subjected to a post-treatment operation such as extraction with an organic solvent and concentration to isolate the desired compound. Further, the target compound can be purified by recrystallization, chromatography or the like.
  • the triazolone compound represented by the formula [L] can be represented as a tautomer shown below.
  • 2-Methylsemicarbazide can be produced, for example, according to the following chemical reaction formula.
  • M 3 represents sodium or potassium.
  • the reaction is usually performed in an acidic aqueous solution (for example, hydrochloric acid).
  • an acidic aqueous solution for example, hydrochloric acid
  • 2-methylsemicarbazide can be produced by reacting trimethylsilyl isocyanate in which M 3 is represented by a trimethylsilyl group with methylhydrazine, and then reacting the reaction product with methanol.
  • Manufacturing method H
  • H-1) A process for producing the compound of the present invention represented by the formula [1-2], wherein R 1 in the formula [I] is an optionally substituted phenyl group, naphthyl group or heterocyclic group.
  • R 8 represents a phenyl group, a naphthyl group or a heterocyclic group, and the phenyl group, the naphthyl group and the heterocyclic group are each a halogen atom, a cyano group, a nitro group, a C 1-(: 10 Alkyl group, C1-C10 haloalkyl group, C3-(: 10 cycloalkyl group, C1-(: 10 alkoxy group, C1-C10 haloalkoxy group, C1-C10 alkylthio group, C1- C 10 haloalkylthio group, (C 1 -C 9 alkyl) carbonyl group, (C 1 -C 9 alkoxy) carbonyl group, (C 1 -C 9 alkyl) capillonylamino group, phenyl group, phenoxy group, benzyloxy group , C 3 It may be substituted with one or more substituents selected from the group consist
  • X and Z are the same or different and represent a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group, and T has the same meaning as described above.
  • the borate compound represented by the formula [XXVIII] is obtained by combining a compound represented by the formula [1-1] with bis (pinacolato) diboron in an organic solvent (for example, dimethyl sulfoxide, dimethylformamide), and a base (for example, , Potassium acetate, potassium carbonate, and a palladium catalyst (for example, a dichloromethan complex of [bis (diphenylphosphino) phene] dichloropalladium (II), tetrakistriphenylphosphine palladium).
  • an organic solvent for example, dimethyl sulfoxide, dimethylformamide
  • a base for example, Potassium acetate, potassium carbonate
  • a palladium catalyst for example, a dichloromethan complex of [bis (diphenylphosphino) phene] dichloropalladium (II), tetrakistriphenylphosphine palladium.
  • the target compound can be purified by chromatography or the like.
  • the compound of the present invention represented by the formula [1-2] is obtained by combining a borate ester compound represented by the formula [XXVIII] and a compound represented by the general formula R 8 Z in an organic solvent (for example, dimethoxetane) with a base (For example, potassium phosphate, potassium carbonate) and a palladium catalyst (for example, [bis (diphenylphosphino) phenoctene] dichloromethane complex of dichloropalladium (II), palladium (II) acetate, tetrakistriphenyl Phosphine palladium, a mixture thereof).
  • an organic solvent for example, dimethoxetane
  • a base for example, potassium phosphate, potassium carbonate
  • a palladium catalyst for example, [bis (diphenylphosphino) phenoctene] dichloromethane complex of dichloropalladium (II), palladium (II) acetate,
  • the solvent is distilled off, and the residue is subjected to chromatography or a post-treatment such as extraction with an organic solvent and concentration to obtain the target compound.
  • the compound can be purified by recrystallization, chromatography and the like.
  • a 3 —C ⁇ C represents an optionally substituted C 2 -C 10 alkynyl group having a terminal triple bond.
  • the alkynyl group is a halogen atom, a cyano group, a nitro group, a C1-C10 alkoxy group, a C1-C10 haloalkoxy group, a C1-C10 alkylthio group, a C1-C 10 haloalkylthio group, (C 1 -C 9 alkylyl) carbonyl group, (C 1 -C 9 alkoxy) carbonyl group, (C 1 -C 9 alkyl) caprolponylamino group, phenyl group, phenoxy group, benzyloxy group and C It may be substituted with one or more substituents selected from the group consisting of 3-C20 trialkylsilyl groups. T and X have the same meaning as described above. ]
  • the reaction of obtaining the compound of the present invention represented by the formula [1-3] from the compound represented by the formula [1-1] is carried out, for example, in an aprotic polar solvent (for example, acetonitrile, N, N-dimethylformamide).
  • aprotic polar solvent for example, acetonitrile, N, N-dimethylformamide.
  • Base eg, secondary amine such as diisopropylamine, tertiary amine such as triethylamine
  • catalyst eg, palladium catalyst such as bis (triphenylphosphine) dichloropalladium ⁇ PdCl 2 (PPh 3 ) 2 ⁇ ; iodide (A combination of copper (I) and triphenylphosphine).
  • the reaction mixture is subjected to post-treatment operations such as extraction with an organic solvent and concentration to obtain a target compound.
  • the target compound can be purified by recrystallization, chromatography and the like.
  • the reaction of obtaining the compound of the present invention represented by the formula [1-2] from the compound represented by the formula [1-1] is carried out, for example, by reacting a base (for example, an inorganic base such as baking soda) in a mixed solvent of water and dimethoxyethane.
  • a base for example, an inorganic base such as baking soda
  • a catalyst for example, tetrakis (triphenyl) phosphine palladium ⁇ Pd (PPh 3 ) 4 ⁇
  • a base eg, an inorganic base such as potassium carbonate
  • a catalyst eg, palladium acetate
  • the reaction mixture is subjected to post-treatment operations such as extraction with an organic solvent and concentration to obtain a target compound.
  • the target compound can be purified by recrystallization, chromatography and the like. If necessary, for example, reference can be made to J. Org. Chem., 62, 7170-7173 (1997).
  • Alpha 4 is phenyl group, naphthyl group or a heterocyclic group
  • the Hue group, a naphthyl group and heterocyclic groups are each, halogen atom , Cyano group, nitro group, C :!
  • the reaction for obtaining the compound of the present invention represented by the formula ⁇ -5] from the compound represented by the formula [1-4] is carried out in an organic solvent (eg, methylene chloride) in a base (eg, an organic base such as triethylamine, baking soda). Etc.) and a catalyst (eg, copper (II) acetate). If necessary, Tetrahedron Lett., 39, 2937-2940 (1998) can be referred to.
  • the compound of the present invention represented by the formula [1-5] is obtained from the compound represented by the formula [1-1].
  • the reaction is carried out with a base (eg, an organic base such as triethylamine, an inorganic base such as potassium carbonate or cesium carbonate) and a catalyst (eg, copper (I) iodide) in an organic solvent (eg, toluene, ethyl acetate).
  • a base eg, an organic base such as triethylamine, an inorganic base such as potassium carbonate or cesium carbonate
  • a catalyst eg, copper (I) iodide
  • an organic solvent eg, toluene, ethyl acetate
  • the target compound can be purified by recrystallization, chromatography and the like.
  • J. Amer. Chem. Soc., .9, 10539-10540 (1997), J. Amer. Chem. Soc., UA, 3224-3
  • the reaction for obtaining the compound of the present invention represented by the formula [1-5] from the compound represented by the formula [XXVIII] is carried out in an organic solvent (eg, methylene chloride) in a base (eg, an organic base such as triethylamine, baking soda).
  • a base eg, an organic base such as triethylamine, baking soda.
  • the reaction can be carried out in the presence of an inorganic base) and a catalyst (eg, copper (II) acetate). If necessary, the description of Tetrahedron Lett., 39, 2937-2940 (1998) can be referred to.
  • a 5 represents a group other than a hydrogen atom among the groups represented by A 1 , and L 2 , A 2 and T have the same meanings as described above.
  • the compound in which A 2 is a methyl group is more, for example, J. Org. Chem., 57, 1481-1486 (1992) than the compound represented by the formula [I-6].
  • Other compounds can also be produced by a conventional method according to the above scheme.
  • each step of the above scheme can be performed according to a conventional method.
  • the compound of the present invention when used as an active ingredient of a fungicide, it may be used as it is without adding any other components, but is usually mixed with a solid carrier, a liquid carrier, a surfactant, and other formulation auxiliaries. , Emulsions, wettable powders, wettable powders, emulsion preparations, flowable preparations, powders, granules and the like. These preparations usually contain the present compound as an active ingredient in an amount of 0.1 to 90% by weight.
  • Examples of the solid carrier used in the formulation include minerals such as kaolin clay, Atsuya pulgite clay, bentonite, montmorillonite, acid clay, pierced fillet, talc, diatomaceous earth, calcite, corn cob powder, and kur Fine powders or granular materials such as natural organic substances such as husk powder, synthetic organic substances such as urea, salts such as calcium carbonate, ammonium sulfate, and synthetic inorganic substances such as synthetic hydrous silicon oxide are used.
  • minerals such as kaolin clay, Atsuya pulgite clay, bentonite, montmorillonite, acid clay, pierced fillet, talc, diatomaceous earth, calcite, corn cob powder, and kur Fine powders or granular materials
  • natural organic substances such as husk powder
  • synthetic organic substances such as urea
  • salts such as calcium carbonate, ammonium sulfate
  • synthetic inorganic substances
  • Aromatic hydrocarbons such as xylene, alkylbenzene and methylnaphthylene, alcohols such as isopropanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ketones such as acetone, cyclohexanone and isophorone; Vegetable oils such as soybean oil, cottonseed oil, Aliphatic hydrocarbons, esters, dimethyl sulfoxide, Aseto nitrile, water and the like.
  • surfactants include, for example, alkyl sulfates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates, lignin sulfonates, and formalin condensates of naphthalene sulfonate.
  • Nonionic surfactants such as ionic surfactants, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl polyoxypropylene block copolymers, and sorbin fatty acid esters.
  • compositions include, for example, water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone, gum arabic, alginic acid and its salts, polysaccharides such as CMC (potassium oxymethylcellulose), xanthan gum, aluminum magnesium silicate, alumina sol And the like, preservatives, coloring agents, stabilizers such as PAP (isopropyl acid phosphate), and BHT.
  • water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone
  • gum arabic alginic acid and its salts
  • polysaccharides such as CMC (potassium oxymethylcellulose), xanthan gum, aluminum magnesium silicate, alumina sol And the like
  • preservatives such as CMC (potassium oxymethylcellulose), xanthan gum, aluminum magnesium silicate, alumina sol And the like
  • preservatives such as PAP (isopropyl acid phosphate)
  • PAP isoprop
  • the application method of the compound of the present invention include foliage application, soil treatment, seed disinfection, and the like. Further, it can be used in any application method usually used by those skilled in the art.
  • the application rate of the active ingredient depends on the type of the target plant (crop, etc.), the type of the target disease, the degree of occurrence of the disease, the formulation, the application method, and the application. Although it may vary depending on the timing, weather conditions, etc., it is usually l to 500 g, preferably 5 to 100 g per hectare.
  • Emulsion, water When diluting a wetting agent, suspending agent or the like with water and applying the active ingredient, the application concentration of the active ingredient is 0.001 to 3% by weight, preferably 0.005 to 1% by weight, Powders, granules, etc. are applied without dilution.
  • the compound of the present invention can be used as a fungicide for agricultural and horticultural use in fields, paddy fields, orchards, tea gardens, pastures, lawns, etc., and can be used in combination with other fungicides for agricultural and horticultural use. Can be expected to increase.
  • Other agricultural and horticultural fungicides that can be mixed are, for example, propiconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromconazole, epoxyconazole, diphenoconazole, cyproconazole.
  • Metconazole triflumizole, tetraconazole, microbudinil, fenbuconazole, hexaconazole, fluquinconazole, triconazol, Vitelenol, ipconazole, imibenconazole, imazalil and flutriahole, etc.
  • Azole fungicides, cyclic amine fungicides such as fenpropimorph, tridemorph and fenpropidine, carbendazim, benomyl, thiabendazole, thiophanate methyl, etc.
  • Disimidazol-based germicidal compounds ethylene biscarbamate-based compounds such as maneb, zineb, mancozeb, etc., phthalimide-based compounds such as capbutane and folpette, basic copper chloride, basic copper sulfate, copper sulfate, cupric hydroxide, Inorganic copper such as copper 8-hydroxyquinoline, copper nonylphenol sulphonate, etc., procymidone, cyprodinil, pyrimethanil, dietofencalp, thiuram, fluazinam, iprodione, vinclozolin, chlorothalonil, mepanipyrim, fenpiclonil, fludicloxonil di, , Folpet, Klesoxim-methyl, Azoxycistrobin, Trifloxystrobin, Picoxystrobin, N-Methyl- ⁇ -Methoxyimino 2-([(2,5-Dimethylphenoxy) methyl) Phenyl ace
  • the mixing ratio of the active compound of the present invention and the azole fungicide is not particularly limited, but 1 part by weight of the compound of the present invention is added to the azole fungicide. Is particularly excellent when the content is in the range of 0.25 to 4 parts by weight.
  • the mixing ratio of the compound of the present invention, which is an active ingredient, and the cyclic amine fungicidal compound is not particularly limited, but is preferably 1 part by weight of the compound of the present invention.
  • the amount of the cyclic amine fungicide is in the range of 1 to 8 parts by weight, a particularly excellent synergistic effect is exhibited.
  • the mixing ratio of the compound of the present invention, which is an active ingredient, to quinoxyfen is not particularly limited, but 0.25 to 1 part by weight of the compound of the present invention.
  • Particularly excellent synergistic effects are exhibited when the content is in the range of 2 to 2 parts by weight.
  • the mixing ratio of the compound of the present invention, which is an active ingredient, to spiroxamine is not particularly limited, but 1 to 8 parts by weight of spiroxamine is used per 1 part by weight of the compound of the present invention. When the ratio is in the range, a particularly excellent synergistic effect is exhibited.
  • the mixing ratio of the compound of the present invention and the ethylene biscarbamate compound which is an effective component is not particularly limited, but is 1 part by weight of the compound of the present invention.
  • the ethylene biscarbamate compound is in the range of 1 to 20 parts by weight, a particularly excellent synergistic effect is exhibited.
  • the mixing ratio of the active compound of the present invention and the phthalimide compound is not particularly limited, but the phthalimide compound is added to 1 part by weight of the compound of the present invention. Is particularly excellent when the content is in the range of 1 to 20 parts by weight.
  • the mixing ratio of the compound of the present invention, which is an active ingredient, and inorganic copper or organic copper is not particularly limited.
  • the compound of the present invention can be mixed with other agricultural and horticultural insecticides, acaricides, nematicides, herbicides, plant growth regulators, and fertilizers, or can be simultaneously applied without application.
  • insecticides examples include, for example, phennitrothion [ ⁇ , ⁇ -dimethyl-1- (3-methyl_412-trophenyl) phosphorothioate], phenithion [0, ⁇ -dimethyl ⁇ _ (3 —Methyl-4- (methylthio) phenyl) phosphorothioate], diazinon [ ⁇ , ⁇ getyl ⁇ ⁇ —2 ⁇ sopropyl— 6-methylpyrimidine—4-yl phosphorothioate], chlorpyrifos [ ⁇ , O— Getyl O—3,5,6-trichloro mouth—2 monopyridyl phosphorothioate], acephate ( ⁇ , S-dimethylacetyl phosphoramide), methidathion (S—2,3-dihydro— 5-Methoxy-2-iso-1,3,4-thiadiazole-3-ylmethyl ⁇ , O-dimethyl phosphoramide
  • Rice blast (Pyricularia oryzae), Sesame leaf blight (Cochl iobolus miyab eanus), Sheath blight (Rhizoctonia solani), Mustard powdery mildew (Erys iphe gra minis), Red rot (Gibberel la zeae) ), Sabi Byung (Puccinia stri i formis, P. graminis, P. recondi ta, P. hordei)> Snow rot (Typhula sp., Micronectriel 1 a nivalis), Naked smut (Ustilago tritici, U.
  • Black smut (Till etia caries)> Eye spot disease (Pseudocercosporella herpotr ichoides), scald disease (Rh ynchosporium secal is), leaf blight (Septor ia tritici), blight (Leptosphae ria nodorum), citrus black spot , Disease (Diaporthe citri), scab (Elsinoe fawcetti), fruit rot (Penici 11 ium digitatum, P.
  • Kidney anthracnose Col letotr ichum 1 indemthianuin
  • Black spot of Laccasey Cercospora
  • brown spot Cercospora arachidicola
  • endo powdery mildew Erysi phe pisi
  • summer sickness of swords Alternaria solani
  • plague Phytophthora infestans
  • powdery mildew of strawberry Sphaerotheca humuli
  • scab rot Exobasidium reti culatum
  • white scab Elsinoe leucos lapi)
  • Tobacco scab Alternaria Ion gipes;, Powdery mildew (Erysiphe cichoracearum), Anthracnose (Col letotrichum t abacum;), Beto; 3 ⁇ 4 (Peronospora tabacina), Phytophthora nicot iana e), Sugar beet Brown spot (Cercospora bet
  • Production Examples of the compound of the present invention and Production Examples of intermediates for producing the compound of the present invention are shown in Production Examples, Reference Production Examples, and Production Examples of Intermediates.
  • the numbers of the compounds of the present invention are represented by the compound numbers shown in Tables 1 to 17 below.
  • the zeolite powder remaining after filtration was washed with 90% methanol water (2.2 L ⁇ 2 times), the filtrate and the washing solution were combined, and the mixture was concentrated until the total liquid volume became about 750 ml.
  • the resulting white crystals were filtered, and the crystals were washed with water to obtain 162 g (826 mmol) of 5-bromo-2-methylbenzonitrile.
  • reaction solution was extracted with t-butyl methyl ether, and the organic layer was washed with water, saturated aqueous sodium hydrogen carbonate, and then with saturated saline, dried over anhydrous magnesium sulfate, and concentrated, and concentrated to 2-methyl-5-phenylbenzyl alcohol 12 lg. I got
  • 5-bromo_2-methylbenzonitrile (produced in the same manner as (1) of Reference Production Example 1) was prepared by dissolving 81.7 g (417 mmol) in 50 mL of anhydrous toluene.
  • 50 Oml (50 Ommol) of a toluene solution of diisobutylaluminum hydride (1.0 M) was added dropwise, and the mixture was stirred at room temperature with stirring.
  • 15 ml of ethyl acetate was added dropwise to the reaction solution, and this was poured into a mixture of 2 L of ice water and 170 ml of concentrated hydrochloric acid.
  • reaction solution was extracted with t-butyl methyl ether, and the organic layer was washed with water, twice with saturated aqueous sodium bicarbonate, then with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give 5-promo 2 —168 g of methylbenzyl alcohol were obtained.
  • 2-Methyl-4_ (2-methyl-5-phenylbenzyl) semicarbazide (prepared in the same manner as in Intermediate Preparation Example 4) A solution prepared by dissolving 300 mg (l. Under an atmosphere, 180 ml (1.45 mmol) of ethyl difluoroacetate and 0.23 ml (1.1 mmol) of a 28% methanol solution of sodium methoxide were added. The mixture was stirred under heating and reflux for 9 hours, and cooled to room temperature. After adding 20 ml of water to the reaction solution, 2 N hydrochloric acid was added to adjust the pH to 1, and the mixture was extracted with ethyl acetate.
  • 1-Difluoroacetyl-2-methyl-4 _ (2-methyl-5-phenylbenzyl) semicarbazide (produced in the same manner as in Production Example 27) 146 mg (0.420 bandage 01) of 2% by weight hydroxylated The mixture was added to 2 ml of an aqueous potassium solution, and the mixture was stirred under reflux for 3 hours. After the reaction solution was cooled to room temperature, 2 N hydrochloric acid was added to adjust the pH to 3, followed by extraction with ethyl acetate.
  • reaction solution was stirred under heating to reflux for 18 hours and concentrated.
  • Ethyl acetate was added to the residue, and the mixture was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated.
  • N, N-dimethyl- (2-methyl-5-phenylpentyl) amine (Prepared in the same manner as in Preparation Example 12) 31 To a solution of 5 mg (1.4 Ommo 1) dissolved in toluene 3 ml At room temperature, methyl methyl carbonate 37 Omg (3.92 mmol) was slowly added dropwise. Immediately after the addition, the reaction mixture became cloudy. After stirring this cloudy liquid at room temperature for 7 hours, it was washed successively with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate, and concentrated.
  • Each wettable powder is obtained by thoroughly pulverizing and mixing 50 parts of each of the present compounds 1 to 438, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide.
  • Each emulsion is obtained by thoroughly mixing 5 parts of each of the present compounds 1 to 438, 14 parts of polyoxyethylenestyrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.
  • Formulation Example 5 2 parts of each of the compounds of the present invention 1 to 438, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay, are well pulverized and mixed, and water is added and kneaded well. Then, each granule is obtained by granulation and drying.
  • Test Examples 1 to 6 are tests in which a large amount of spray solution (about 2000 LZha) was applied to plants, and spraying was performed so that the plant surface was completely wetted and the chemical solution dripped off. 'is there.
  • Test examples 7 and 8 are tests using a small amount of spray liquid (equivalent to 200 LZ ha) on plants, and the spray liquid was uniformly attached to the surface of the plant with fine droplets. Insufficient spraying to completely wet the plant surface.
  • Control of wheat disease in the field may be performed with a spray volume of around 200 LZha.
  • the applied chemical liquid has an insufficient amount to wet the whole plant, and is attached as fine droplets on the plant.
  • it is necessary to have suitable physicochemical properties such as systemic transferability and volatility in addition to the high basic efficacy of the active ingredient. is there.
  • the compounds of the present invention are represented by the compound numbers shown in Tables 1 to 18.
  • the control effect of the compound of the present invention is determined by measuring the area of the lesion on the test plant at the time of the survey. It was evaluated by observing with eyes and comparing the area of the lesion in the untreated section with the area of the lesion in the section treated with the compound of the present invention.
  • Test example 1 Rice blast control test
  • Plastic pots were filled with sandy loam, rice (Nipponbare) was sown, and grown in a greenhouse for 20 days. Thereafter, the compounds of the present invention 1, 3, 4, 6, 7, 9, 18, 19, 20, 24, 47, 104, 105, 113, 117, 118, 120, 294, 326, 329, 343 And 345 were each made into a flooring agent in accordance with Formulation Example 6, diluted with water to a predetermined concentration, and sprayed with foliage so as to sufficiently adhere to the rice leaf surface. After spraying, the plants were air-dried and sprayed with a suspension of the blast fungus. After inoculation, the plants were placed in a humid environment at 28 ° C for 6 days, and the control effect was investigated. As a result, the lesion area on the plants in the 50 Oppm and 200 ppm treatment groups of the present compound 1 was 10% or less of the lesion area in the untreated group.
  • Test example 2 Wheat powdery mildew control test
  • Plastic pots were filled with sandy loam, and wheat (Norin 73) was sowed and grown in a greenhouse for 10 days.
  • Compounds of the Invention 1, 3, 4, 6, 7, 9, 18, 19, 20, 24, 47, 104, 105, 113, 117, 118, 120, 277, 294, 326, 329, 343 And 345 were prepared as floor pills according to Formulation Example 6, and then diluted to a predetermined concentration with water.Then, the 345 was diluted so that it adhered sufficiently to the wheat leaf surface of the wheat seedlings in which the second leaves had developed. Foliage was sprayed. After spraying, the plants were air-dried. One day later, wheat spores were sprinkled and inoculated. After inoculation, the plants were placed under 23 ° C light for 7 days, and the control effect was examined.
  • the lesion area on the plants in the 50 Oppm and 20 Oppm treatment sections of the present compound 1 was 10% or less of the lesion area in the non-treatment section.
  • Test example 3 Wheat rust control test
  • Plastic pots were filled with sandy loam, and wheat (Norin 73) was sowed and grown in a greenhouse for 10 days.
  • Compounds of the present invention 1, 3, 4, 6, 7, 9, 18, 19, 20, 24, 47, 104, 105, 113, 1117, 118, 120, 277, 294, 326, 329, Each of 343 and 345 was prepared as a flooring agent according to Preparation Example 6, then diluted with water to a predetermined concentration, and sprayed with foliage so as to sufficiently adhere to the leaves of the wheat. After spraying, the plants were air-dried and inoculated with spores of wheat rust. After inoculation, the plants were placed in a dark and humid environment at 23 ° C for 1 day, and then put under lighting for 6 days.
  • the lesion area on the plants in the 50 Oppm and 20 Oppm treatment sections of the present compound 1 was 10% or less of the lesion area in the non-treatment section.
  • the lesion area on the plant in each of the treated sections at 20 Oppm in each of 7, 118, 120, 277, 294, 326, 329, 343, and 345 was less than 10% of the lesion area in the untreated section.
  • Test example 4 Wheat blight control test
  • Plastic pots were filled with sandy loam, sown with wheat (Norin 73), and grown in a greenhouse for 10 days.
  • Formulation Examples of Compounds 1, 3, 4, 6, 7, 9, 18, 19, 20, 24, 47, 104, 105, 113, 118, 120, 277, 329, 343, 345 of the Compounds of the Present Invention After making it a flowable agent according to 6, it was diluted to a predetermined concentration with water, and this was sprayed with foliage so as to sufficiently adhere to the wheat leaf surface. After spraying, the plants were air-dried and sprayed with a spore suspension of wheat wilt. After the inoculation, they were initially placed 15 days in the dark and humid for 4 days, and then placed in the light for 7 days.
  • the lesion area on the plants in the 500 ppm and 200 ppm treatment groups of the present compound 1 was 10% or less of the lesion area in the untreated group.
  • Compounds of the invention 3 4, 6, 7, 9, 18, 19, 20, 24, 47, 104, 105, 1 13, 1 1
  • the lesion area on plants in the 200 ppm treated areas of 8, 120, 277, 329, 343, and 345 was less than 10% of the lesion area in the untreated area.
  • Test example 5 Grape downy mildew control effect test Plastic pots were filled with sandy loam, sown with grapes (berry A), and grown in a greenhouse for 40 days. Compounds of the present invention 1, 3, 4, 6, 7, 9, 18, 19, 20, 24, 47, 104, 105, 113, 117, 118, 1 2 Each of 0, 277, 294, 326, 329, 343, and 345 was made into a flouropul according to Formulation Example 6, and then diluted with water to the specified concentration (20 Opm) This was sprayed with foliage so as to sufficiently adhere to the leaf surface of the grape. After spraying, the plants were air-dried and spray-inoculated with a zoospore suspension of grape downy mildew. After the inoculation, the plants were placed at 23 ° C and a high humidity for 1 day, and then placed in a greenhouse for 6 days.
  • the compounds of the present invention 1, 3, 4, 6, 7, 9, 18, 18, 19, 20, 24, 47, 104, 105, 113, 117, 118, 12 0, 2 7 7, 2 94, 3 26, 3 29, 3 43, 3 4 5
  • the area of the lesion on the plant in the treated area was less than 10% of the area of the lesion in the untreated area.
  • Test Example 6 Test for control effect of powdery mildew on cucumber
  • Plastic pots were filled with sandy loam, sown with Kiuri (Sagami Hanjiro), and grown for 12 days in a greenhouse.
  • Compound 1 of the present invention was made into a flowable agent according to Formulation Example 6, then diluted with water to a predetermined concentration (20 Oppm), and sprayed with foliage so as to sufficiently adhere to the leaves of the cucumber. After spraying, the plants were air-dried and inoculated with the spores of the powdery mildew fungus. After the inoculation, they were placed under 23 for 12 days, and the control effect was investigated. As a result, the lesion area on the plant in the section treated with the compound of the present invention 1 was 10% or less of the lesion area in the untreated section.
  • Test Example 7 Wheat powdery mildew control effect test
  • Plastic pots were filled with sandy loam, and wheat (Norin 73) was sowed and grown in a greenhouse for 10 days.
  • Compound 1 of the present invention was made into an emulsion according to Formulation Example 7, and then diluted with water to a predetermined concentration (100 Op pm). The foliage was sprayed at a spray liquid amount equivalent to 0 OL / ha. After spraying, the plants were air-dried and sprinkled with wheat powdery mildew spores one day later. After inoculation, the plants were placed under 23 ° C lighting for 7 days, and the control effect was examined.
  • Test Example 8 Wheat rust control test
  • Compound 1 of the present invention was made into an emulsion according to Formulation Example 7, and then diluted with water at a predetermined concentration (100 ppm), and sprayed on the wheat seedlings, in which the second leaves had developed, equivalent to 200 LZha. The foliage was sprayed at the liquid volume. After spraying, the plants were air-dried and inoculated with spores of wheat rust. Initially after inoculation, it was kept at 23 ° (:, dark and humid for 1 day, and then put under lighting for 6 days, and the control effect was investigated.
  • the compound of the present invention has excellent bactericidal efficacy.

Abstract

L'invention concerne des composés de triazolone représentés par la formule générale (I), des fongicides dans lesquels ces composés tiennent lieu de principe actif; et des intermédiaires pour la fabrication des composés en question. Dans ladite formule, R1 est phényle éventuellement substitué ou autre; et T est m-phénylène éventuellement méthylé ou autre.
PCT/JP2000/008558 1999-12-08 2000-12-01 Composes de difluoromethyltriazolone, utilisation de ces composes et intermediaires pour leur fabrication WO2001042227A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/149,034 US6762197B2 (en) 1999-12-08 2000-12-01 Difluoromethyltriazolone compounds, use of the same and intermediates for the production thereof
EP00979060A EP1238975A1 (fr) 1999-12-08 2000-12-01 Composes de difluoromethyltriazolone, utilisation de ces composes et intermediaires pour leur fabrication
AU16510/01A AU1651001A (en) 1999-12-08 2000-12-01 Difluoromethyltriazolone compounds, use of the same and intermediates for the production thereof

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP34888499 1999-12-08
JP11-348884 1999-12-08
JP2000-110682 2000-04-12
JP2000110682 2000-04-12
JP2000164223 2000-06-01
JP2000-164223 2000-06-01
JP2000-240866 2000-08-09
JP2000240866A JP2002053561A (ja) 1999-12-08 2000-08-09 ジフルオロメチルトリアゾロン化合物、その用途およびその製造中間体

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US10/149,034 A-371-Of-International US6762197B2 (en) 1999-12-08 2000-12-01 Difluoromethyltriazolone compounds, use of the same and intermediates for the production thereof
US10/781,988 Division US20040167193A1 (en) 1999-12-08 2004-02-20 Difluoromethyltriazolone compounds, use of the same and intermediates for the production thereof

Publications (1)

Publication Number Publication Date
WO2001042227A1 true WO2001042227A1 (fr) 2001-06-14

Family

ID=27480694

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2000/008558 WO2001042227A1 (fr) 1999-12-08 2000-12-01 Composes de difluoromethyltriazolone, utilisation de ces composes et intermediaires pour leur fabrication

Country Status (5)

Country Link
US (2) US6762197B2 (fr)
EP (1) EP1238975A1 (fr)
JP (1) JP2002053561A (fr)
AU (1) AU1651001A (fr)
WO (1) WO2001042227A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020027214A1 (fr) 2018-07-31 2020-02-06 住友化学株式会社 PROCÉDÉ DE LUTTE CONTRE LA ROUILLE DU SOJA RÉSISTANT AUX INHIBITEURS DE Qo

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006076990A (ja) * 2004-03-12 2006-03-23 Bayer Cropscience Ag 殺虫性ベンゼンジカルボキサミド類
TW200840566A (en) * 2006-12-22 2008-10-16 Esteve Labor Dr Heterocyclyl-substituted-ethylamino-phenyl derivatives, their preparation and use as medicaments
WO2009158011A1 (fr) * 2008-06-26 2009-12-30 Amgen Inc. Alcools d’alcynyle utilisés comme inhibiteurs de kinases
WO2014089140A1 (fr) 2012-12-05 2014-06-12 Merck Sharp & Dohme Corp. Procédé de préparation d'inhibiteurs de transcriptase inverse
BR112015029998A2 (pt) * 2013-06-27 2017-07-25 Basf Se compostos de fórmula, composição agroquímica, método para o combate dos fungos nocivos fitopatogênicos, utilização dos compostos de fórmula e semente
WO2015191382A1 (fr) * 2014-06-11 2015-12-17 E. I. Du Pont De Nemours And Company Tétrazolinones fongicides
US11192854B2 (en) * 2018-06-12 2021-12-07 Tokuyama Corporation Method for producing semicarbazide compound
AR121209A1 (es) * 2020-01-31 2022-04-27 Sumitomo Chemical Co Método para controlar hongos de la roya de la soja que tienen resistencia contra el inhibidor de sitio qo

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994024116A1 (fr) * 1993-04-09 1994-10-27 Syntex Pharmaceuticals Limited Derives heterocycliques utilises dans le traitement de l'ischemie et d'autres pathologies associees
WO1999007687A1 (fr) * 1997-08-05 1999-02-18 Agrevo Uk Limited Derives pesticides de 4-benzyl-1,2,4-triazolin-5-one
WO1999010317A1 (fr) * 1997-08-26 1999-03-04 Kumiai Chemical Industry Co., Ltd. Derives d'acide biarylalkylenecarbamique et bactericides a usage horticole et agricole
WO2000007999A1 (fr) * 1998-08-03 2000-02-17 Sumitomo Chemical Company, Limited Derives de triazolone, leur utilisation, et produits intermediaires obtenus a partir de ces derives

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4473709A (en) 1980-07-14 1984-09-25 Fmc Corporation Pyrethroid intermediates and process
DE4339412A1 (de) 1993-11-18 1995-05-24 Bayer Ag Verfahren und neue Zwischenprodukte zur Herstellung von Triazolinonen
DE4342190A1 (de) 1993-12-10 1995-06-14 Bayer Ag Verfahren und neue Zwischenprodukte zur Herstellung von Triazolinonen
JPH1045754A (ja) 1996-08-01 1998-02-17 Otsuka Chem Co Ltd １，２，４−トリアゾール誘導体及び該誘導体を含有する除草剤
DE19834557A1 (de) 1998-07-31 2000-02-03 Basf Ag (Hetero)Arylverbindungen, Verfahren und Zwischenprodukte zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von Schadpilzen und tierischen Schädlingen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994024116A1 (fr) * 1993-04-09 1994-10-27 Syntex Pharmaceuticals Limited Derives heterocycliques utilises dans le traitement de l'ischemie et d'autres pathologies associees
WO1999007687A1 (fr) * 1997-08-05 1999-02-18 Agrevo Uk Limited Derives pesticides de 4-benzyl-1,2,4-triazolin-5-one
WO1999010317A1 (fr) * 1997-08-26 1999-03-04 Kumiai Chemical Industry Co., Ltd. Derives d'acide biarylalkylenecarbamique et bactericides a usage horticole et agricole
WO2000007999A1 (fr) * 1998-08-03 2000-02-17 Sumitomo Chemical Company, Limited Derives de triazolone, leur utilisation, et produits intermediaires obtenus a partir de ces derives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020027214A1 (fr) 2018-07-31 2020-02-06 住友化学株式会社 PROCÉDÉ DE LUTTE CONTRE LA ROUILLE DU SOJA RÉSISTANT AUX INHIBITEURS DE Qo

Also Published As

Publication number Publication date
JP2002053561A (ja) 2002-02-19
US20030119670A1 (en) 2003-06-26
US6762197B2 (en) 2004-07-13
AU1651001A (en) 2001-06-18
US20040167193A1 (en) 2004-08-26
EP1238975A1 (fr) 2002-09-11

Similar Documents

Publication Publication Date Title
JP6237646B2 (ja) テトラゾリノン化合物及びその用途
JP6323450B2 (ja) テトラゾリノン化合物及びその用途
JPH10310577A (ja) 置換カルボン酸アニリド誘導体およびこれを有効成分とする植物病害防除剤
JPH10130268A (ja) 置換チオフェン誘導体およびこれを有効成分とする農園芸用殺菌剤
JP2000226374A (ja) ピラゾリノン誘導体
WO2001042227A1 (fr) Composes de difluoromethyltriazolone, utilisation de ces composes et intermediaires pour leur fabrication
JP2002308879A (ja) ５−ハロアルキル−アゾロピリミジン化合物、製造方法及び有害生物防除剤
US5763475A (en) Method of control plant disease
WO1998043949A1 (fr) Composes d'ether d'oxime, leur utilisation et intermediaires pour leur preparation
JP2001114737A (ja) オキシム誘導体及びその用途
JP3780541B2 (ja) 植物病害防除剤
WO2000018727A1 (fr) Intermediaires dans la production de composes d'oxime-ether
US6489487B1 (en) Triazolone derivatives, use thereof, and intermediates therefor
EP0535980B1 (fr) Dérivés de la 2-pyridone, procédé pour leur préparation et leur utilisation comme fongicides
JP5092372B2 (ja) ピリダジン化合物及びそれを含有する殺菌剤
JPH10182642A (ja) 置換チオフェン誘導体およびこれを有効成分とする植物病害防除剤
JP4661163B2 (ja) ６−アリールピリミジノン化合物及びその用途
AU2017333782A1 (en) Novel 5-substituted imidazolylmethyl derivatives
JP2001064237A (ja) アクリル酸誘導体、その用途およびその製造中間体
JPH08301867A (ja) ピラゾリン誘導体、その用途およびその製造中間体
JP2001011053A (ja) ３−ピラゾリン−５−オン化合物及びその用途
JPH05194398A (ja) アクリル酸誘導体、その製造法およびそれを有効成分として含有する植物病害防除剤
WO2000041999A1 (fr) Derives d'oxime et utilisations associees
JP2000239261A (ja) トリアゾロン誘導体、その用途及びその製造中間体
JPH11228567A (ja) 置換チオフェン誘導体およびこれを有効成分とする植物病害防除剤

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2000979060

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10149034

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 2000979060

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 2000979060

Country of ref document: EP